Deuterium-enriched aldehydes

ABSTRACT

The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation. In one aspect, the present invention provides a composition comprising a compound of structure 1: 
                         
wherein: there are at least 6×10 18  molecules of the aldehyde and R x  is hydrogen, wherein the deuterium isotope in R x  is in an amount greater than 0.10 percent of the hydrogen atoms present in R x .

FIELD OF THE INVENTION

The present invention generally relates to deuterium-enriched aldehydes,compositions comprising deuterium-enriched aldehydes, and methods forslowing the rate of aldehyde autoxidation.

BACKGROUND OF THE INVENTION

Aldehydes are organic compounds containing a H—C(O)— moiety. They areused extensively in industrial processes. Formaldehyde, for instance, isproduced on a scale of about 6,000,000 tons/year. Aldehydes are mainlyused in the production of resins, but they also find application asprecursors to plasticizers and other compounds used in the manufacturingof polymers. On a smaller scale, some aldehydes are used as ingredientsin perfumes, flavors and compositions that modulate the behavior ofinsects, e.g., pheromone containing compositions.

Aldehydes have a tendency to react with atmospheric oxygen to formcarboxylic acids (H—C(O)— oxidizes to HO₂C—) in a process known asauto-oxidation or autoxidation. The acids produced by autoxidation canlower the quality and usefulness of aldehyde-containing compositions.

Despite all of the research and development that has been directed topreservation of aldehydes, there is still a need in the art for improvedaldehyde-containing compositions and related methods.

SUMMARY OF THE INVENTION

In an aspect, the present invention provides a novel deuterium-enrichedaldehyde of structure 1:

In another aspect, the present invention provides a novel method ofmaking a deuterium-enriched aldehyde of structure 1.

In another aspect, the present invention provides a novel composition,comprising: a deuterium-enriched aldehyde of structure 1.

In another aspect, the present invention provides a novel composition,comprising: a deuterium-enriched aldehyde of structure 1 and an organicsolvent.

In another aspect, the present invention provides a novel compositionfor modulating the behavior of insects, comprising: a deuterium-enrichedaldehyde of structure 1 and an optional additional component suitablefor the composition.

In another aspect, the present invention provides a novel method ofmanufacturing a resin or polymer using a deuterium-enriched aldehyde ofstructure 1.

These and other aspects, which will become apparent during the followingdetailed description, have been achieved by the inventors' discoverythat deuterium can slow the autoxidation of aldehydes.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a graph comparing the amount of air oxidation ofbenzaldehyde to benzoic acid where the hydrogen atom on the carbonylgroup (i.e., H—C(O)Ph) is enriched in its deuterium isotope (i.e., >95%deuterium, “benzaldehyde-D”) and where it is not enriched (i.e.,naturally occurring isotopic abundance, “benzaldehyde-H”).

FIG. 2 shows a graph comparing the amount of air oxidation of hexanal tohexanoic acid where the hydrogen atom of the carbonyl group (i.e.,H—C(O)C₅H₁₁) is enriched in its deuterium isotope (i.e., >95% deuterium,“hexanal-D”) and where it is not enriched (i.e., naturally occurringisotopic abundance, “hexanal-H”).

DETAILED DESCRIPTION OF THE INVENTION Definitions

All examples provided herein are not intended to be limiting.

“Alkyl” refers to an alkane chemical moiety. The alkanes may be linear,branched, or cyclic. Lower alkyl groups are those that include 1-6carbon atoms. Higher alkyl groups are those that include 7-20 carbonatoms. Cyclic alkyl or cycloalkyl groups include 3-8 carbon atoms.Examples of such moieties include: CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂,CH₂CH₂CH₂CH₃, CH(CH₃)CH₂CH₃, CH₂CH(CH₃)₂, C(CH₃)₃, CH₂CH₂CH₂CH₂CH₃,CH(CH₃)CH₂CH₂CH₃, CH₂CH(CH₃)CH₂CH₃, CH₂CH₂CH(CH₃)₂, CH₂CH₂CH₂CH₂CH₂CH₃,cyclopropyl, cyclobutyl, and cyclopentyl.

“Substituted alkyl” refers to an alkyl group where one or more of thehydrogen atoms have been replaced with another chemical group. Examplesof such other chemical groups include: halo, OH, OR₄ (where R₄ is alower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkylgroup), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups),CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (whereR₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independentlylower alkyl groups), CN, alkenyl, substituted alkenyl, alkynyl,substituted alkynyl, aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

“Halo” refers to Cl, F, Br, or I.

“Alkenyl” refers to a moiety containing only carbon and hydrogen thatincludes at least one double bond. The alkenes may be linear, branched,or cyclic. Lower alkenyl groups are those that include 2-6 carbon atoms.Higher alkenyl groups are those that include 7-20 carbon atoms. Cyclicalkenyl or cycloalkenyl groups include 5-8 carbon atoms. Examples ofsuch moieties include: CH═CH₂; CH═CHCH₃; CH₂CH═CH; CH═CHCH₂CH₃;CH₂CH═CHCH₃; CH₂CH₂CH═CH₂; CH═CHCH₂CH₂CH₃; CH═CHCH(CH₃)₂;CH₂CH═CHCH₂CH₃; CH₂CH₂CH═CHCH₃; CH₂CH₂CH₂CH═CH₂; CH═CHCH₂CH₂CH₂CH₃;CH═CHCH₂CH(CH₃)₂; cyclopentenyl, and cyclohexenyl.

“Substituted alkenyl” refers to an alkenyl group where one or more ofthe hydrogen atoms have been replaced with another chemical group.Examples of such other chemical groups include: CO₂H, CO₂R₆ (where R₆ isa lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkylgroup), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkylgroups), CN, alkyl, substituted alkyl, alkynyl, substituted alkynyl,aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Wherethe replaced hydrogen atom is not on the carbon of the double bond,examples of such other chemical groups further include: halo, OH, OCH₃,CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), and NR₄R₅ (whereR₄ and R₅ are independently lower alkyl groups).

“Alkynyl” refers to refers to a moiety containing only carbon andhydrogen that includes a triple bond. The alkynes may be linear orbranched. Lower alkynyl groups are those that include 2-6 carbon atoms.Higher alkynyl groups are those that include 7-20 carbon atoms. Examplesof such moieties include: C≡CH; C≡CCH₃; CH₂C≡CH; C≡CCH₂CH₃; CH₂C≡CCH₃;CH₂CH₂C≡CH₃; C≡CCH₂CH₂CH₃; CH₂C≡CCH₂CH₃; CH₂CH₂C≡CCH₃; CH₂CH₂CH₂C≡CH;C≡CCH₂CH₂CH₂CH₃; CH₂C≡CCH₂CH₂CH₃; CH₂CH₂C≡CCH₂CH₃; CH₂CH₂CH₂C≡CCH₃;CH₂CH₂CH₂CH₂C≡CH; and, C≡CCH₂CH(CH₃)₂.

“Substituted alkynyl” refers to an alkynyl group where one or more ofthe hydrogen atoms have been replaced with another chemical group.Examples of such other chemical groups include: CO₂H, CO₂R₆ (where R₆ isa lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkylgroup), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkylgroups), CN, alkyl, substituted alkyl, alkenyl, substituted alkenyl,aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Wherethe replaced hydrogen atom is not on the carbon of the triple bond,Examples of such other chemical groups further include: halo, OH, OCH₃,CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄and R₅ are independently lower alkyl groups).

“Heteroalkyl” refers to an alkyl group where at least one of the carbonatoms has been replaced with a heteroatom. Examples of heteroatomsinclude oxygen (“O”), nitrogen (“N”) and sulfur (“S”). The heteroalkanesmay be linear, branched, or cyclic. Lower heteroalkyl groups are thosethat include 1-6 carbons and heteroatoms. Higher heteroalkyl groups arethose that include 7-20 carbons and heteroatoms. Examples of heteroalkylgroups include: CH₂OCH₃; CH₂CH₂OCH₃; CH₂N(R₉)CH₃ (where R₉ is a loweralkyl group); CH₂CH₂N(R₉)CH₃ (where R₉ is a lower alkyl group); CH₂SCH₃;CH₂CH₂SCH₃; tetrahydrofuran, tetrahydropyran, and morpholine.

“Substituted heteroalkyl” refers to a heteroalkyl group where one ormore of the hydrogen atoms has been replaced with another chemicalgroup. The hydrogen atom that is replaced is typically not on a carbonatom directly attached to the heteroatom. Examples of such otherchemical groups include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently loweralkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂,C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈are independently lower alkyl groups), CN, alkyl, aryl, and heteroaryl.

“Aryl” refers to an aromatic group containing only carbon and hydrogen(e.g., C₆H₅ and C₁₀H₈).

“Substituted aryl” refers to an aryl group where at least one of thehydrogen atoms has been replaced with another chemical group. Examplesof such other chemical groups include: halo, OH, OCH₃, CF₃, OCF₃, NH₂,NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ areindependently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a loweralkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN,alkyl, aryl, and heteroaryl.

“Heteroaryl” refers to an aromatic group where at least one of thecarbon atoms has been replaced by a heteroatom. Examples of suchheteroatoms include oxygen (“O”), nitrogen (“N”) and sulfur (“S”).Examples of heteroaryl groups include: C₄H₂O; C₄H₃N; C₄H₂S; and, C₅H₄N.

“Substituted heteroaryl” refers to a heteroaryl group where at least oneof the hydrogen atoms has been replaced with another chemical group.Examples of such other chemical groups include: halo, OH, OCH₃, CF₃,OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ andR₅ are independently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is alower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN,aryl, and heteroaryl.

Aspects

In an aspect, the present invention is directed to a deuterium-enrichedaldehyde of structure 1:

wherein, R_(x) is hydrogen, wherein the deuterium isotope is in anamount greater than 0.10 percent of the R_(x) hydrogen atoms. In certaincases, the deuterium isotope comprises greater than 1% of the R_(x)hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%,70%, 80%, 90%, or 95% percent of the R_(x) hydrogen atoms. R₁, R₂ and R₃are independently selected from hydrogen (where the hydrogen isun-enriched (i.e., naturally occurring) or is enriched in its deuteriumisotope, e.g., more than 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%,80%, 90%, or 95%), alkyl, substituted alkyl, alkenyl, substitutedalkenyl, alkynyl, substituted alkynyl, heteroalkyl, substitutedheteroalkyl, aryl, substituted aryl, heteroaryl, and substitutedheteroaryl. Alternatively, the CR₁R₂R₃ moiety forms a group selectedfrom: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl.Alternatively, the CR₁R₂ moiety forms a group selected from: an alkenyland substituted alkenyl. Alternatively, the CR₁R₂R₃ moiety forms a groupa group selected from: an alkynyl and substituted alkynyl. Optionally,the aldehyde is substituted with C(O)R_(y), wherein R_(y) is hydrogen,wherein the deuterium isotope is optionally present in an amount greaterthan 0.10% of the R_(y) hydrogen atoms, provided that R_(x) isoptionally H when the deuterium isotope is present in an amount greaterthan 0.10% of the R_(y) hydrogen atoms. In certain cases, the deuteriumisotope comprises greater than 1% of the R_(y) hydrogen atoms, orgreater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%percent of the R_(y) hydrogen atoms.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde of structure 1:

wherein, there are at least 6×10¹⁸ molecules of the aldehyde, ofstructure 1. Compositions of the invention will typically comprise atleast 6×10¹⁹ molecules, and may, for example, comprise at least 6×10²⁰molecules, 6×10²¹ molecules, 6×10²² molecules, or 6×10²³ molecules.R_(x) is hydrogen, wherein the deuterium isotope is in an amount greaterthan 0.10 percent of the R_(x) hydrogen atoms. In certain cases, thedeuterium isotope comprises greater than 1% of the R_(x) hydrogen atoms,or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or95% percent of the R_(x) hydrogen atoms. R₁, R₂ and R₃ are independentlyselected from hydrogen (where the hydrogen is un-enriched (i.e.,naturally occurring) or is enriched in its deuterium isotope, e.g., morethan 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%),alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl,substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl,substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively,the CR₁R₂R₃ moiety forms a group selected from: an aryl, substitutedaryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR₁R₂moiety forms a group selected from: an alkenyl and substituted alkenyl.Alternatively, the CR₁R₂R₃ moiety forms a group a group selected from:an alkynyl and substituted alkynyl. Optionally, the aldehyde issubstituted with C(O)R_(y), wherein R_(y) is hydrogen, wherein thedeuterium isotope is optionally present in an amount greater than 0.10%of the R_(y) hydrogen atoms, provided that R_(x) is optionally H whenthe deuterium isotope is present in an amount greater than 0.10% of theR_(y) hydrogen atoms. In certain cases, the deuterium isotope comprisesgreater than 1% of the R_(y) hydrogen atoms, or greater than 2%, 5%,10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_(y)hydrogen atoms.

In another aspect, reference to compositions comprising the “aldehyde ofstructure 1”, means compositions comprising at least 0.1 mole of analdehyde of structure 1. Compositions of the invention may, for example,comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, or 20 moles of analdehyde of structure 1.

In another aspect, reference to compositions comprising the “aldehyde ofstructure 1”, means compositions comprising at least 1 gram of analdehyde of structure 1. Compositions of the invention may, for example,comprise at least 5, 10, 20, 30, 40, 50, 100, 500, or 1,000 grams of analdehyde of structure 1.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde of structure 1:

wherein:

-   there are at least 6×10¹⁸ molecules of the aldehyde;-   R_(x) is hydrogen, wherein the deuterium isotope is present in an    amount greater than 0.10% of the R_(x) hydrogen atoms;-   R₁, R₂ and R₃ are independently selected from hydrogen, alkyl,    substituted alkyl, alkenyl, substituted alkenyl, alkynyl,    substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl,    substituted aryl, heteroaryl, and substituted heteroaryl;-   alternatively, the CR₁R₂R₃ moiety forms a group selected from: an    aryl, substituted aryl, heteroaryl, and substituted heteroaryl;-   alternatively, the CR₁R₂ moiety forms a group a group selected from:    an alkenyl and substituted alkenyl;-   alternatively, the CR₁R₂R₃ moiety forms a group a group selected    from: an alkynyl and substituted alkynyl; and,-   optionally, the aldehyde is substituted with C(O)R_(y), wherein    R_(y) is hydrogen, wherein the deuterium isotope is optionally    present in an amount greater than 0.10% of the R_(y) hydrogen atoms,    provided that R_(x) is optionally H when the deuterium isotope is    present in an amount greater than 0.10% of the R_(y) hydrogen atoms.

The following are examples of aldehydes according to the presentinvention:

-   -   1. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a lower alkyl.    -   2. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a higher alkyl.    -   3. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a substituted alkyl, where the        substituted alkyl is a lower alkyl, and where the one or more        other chemical groups are selected from: halo, OH, OR₄ (where R₄        is a lower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a        lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently        lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl        group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),        C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl        groups), CN, aryl, substituted aryl, heteroaryl, and substituted        heteroaryl.    -   4. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a substituted alkyl, where the        substituted alkyl is a higher alkyl, and where the one or more        other chemical groups are selected from: halo, OH, OR₄ (where R₄        is a lower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a        lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently        lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl        group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),        C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl        groups), CN, aryl, substituted aryl, heteroaryl, and substituted        heteroaryl.    -   5. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a lower alkenyl.    -   6. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a higher alkenyl.    -   7. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a substituted alkenyl, where the        substituted alkenyl is a lower alkenyl, and where the one or        more other chemical groups are selected from: CO₂H, CO₂R₆ (where        R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a        lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently        lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and        substituted heteroaryl.    -   8. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a substituted alkenyl, where the        substituted alkenyl is a higher alkenyl, and where the one or        more other chemical groups are selected from: CO₂H, CO₂R₆ (where        R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a        lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently        lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and        substituted heteroaryl.    -   9. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂        are hydrogen, and R₃ is a lower alkynyl.    -   10. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a higher alkynyl.    -   11. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a substituted alkynyl, where the        substituted alkynyl is a lower alkynyl, and where the chemical        groups are selected from: CO₂H, CO₂R₆ (where R₆ is a lower alkyl        group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),        C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl        groups), CN, aryl, substituted aryl, heteroaryl, and substituted        heteroaryl.    -   12. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a substituted alkynyl, where the        substituted alkynyl is a higher alkynyl, and where the chemical        groups are selected from: CO₂H, CO₂R₆ (where R₆ is a lower alkyl        group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),        C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl        groups), CN, aryl, substituted aryl, heteroaryl, and substituted        heteroaryl.    -   13. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a lower heteroalkyl.    -   14. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a higher heteroalkyl.    -   15. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a substituted heteroalkyl, where the        substituted heteroalkyl is a lower heteroalkyl.    -   16. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is a substituted heteroalkyl, where the        substituted heteroalkyl is a higher heteroalkyl.    -   17. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is aryl.    -   18. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is substituted aryl.    -   19. A deuterium-enriched aldehyde of structure 1, where R₁ and        R₂ are hydrogen, and R₃ is heteroaryl.    -   20. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is aryl.    -   21. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is substituted aryl.    -   22. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is heteroaryl.    -   23. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is substituted heteroaryl.    -   24. A deuterium-enriched aldehyde of structure 1, where CR₁R₂ is        alkenyl and R₃ is hydrogen.    -   25. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is substituted alkenyl and R₃ is hydrogen.    -   26. A deuterium-enriched aldehyde of structure 1, where CR₁R₂ is        alkenyl and R₃ is alkyl.    -   27. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        is substituted alkenyl and R₃ is alkyl.    -   28. A deuterium-enriched aldehyde of structure 1, where R₁ is        alkyl substituted with C(O)R_(y).    -   29. A deuterium-enriched aldehyde of structure 1, where R₁ is        alkyl substituted with C(O)R_(y) and R₂ and R₃ are hydrogens.    -   30. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        aryl substituted with C(O)R_(y).    -   31. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃        substituted aryl substituted with C(O)R_(y).

Additional deuterium-enriched aldehydes of the present invention includethose numbered 2-64 shown below.

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 2% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 10% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 20% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 30% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 40% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 50% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 60% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 70% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 80% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 90% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 2-64 wherein the deuterium isotope in R_(x) is in an amountgreater than 95% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64.

Reference to “compositions comprising compounds 2-64” means compositionscomprising at least 6×10¹⁸ molecules of at least one of aldehydes 2-64,typically at least 6×10¹⁹ molecules, and may, for example, comprise atleast 6×10²⁰ molecules, 6×10²¹ molecules, 6×10²² molecules, or 6×10²³molecules. R_(x) is hydrogen, wherein the deuterium isotope is in anamount greater than 0.10 percent of the R_(x) hydrogen atoms. In certaincases, the deuterium isotope comprises greater than 1% of the hydrogenatoms, or even greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%,80%, 90%, or 95% of the hydrogen atoms.

In another aspect, reference to “compositions comprising compounds 2-64”means compositions comprising at least 0.1 mole of at least one ofaldehydes 2-64. Compositions of the invention may, for example, compriseat least 0.2, 0.5, 1, 2, 3, 4, 5, 10, to 20 moles of at least one ofcompounds 2-64.

In another aspect, reference to “compositions comprising compounds 2-64”means compositions comprising at least 1 gram of at least one ofaldehydes 2-64. Compositions of the invention may, for example, compriseat least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of at least oneof compounds 2-64.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 2%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 10%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 20%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 30%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 40%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 50%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 60%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 70%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 80%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 90%of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64wherein the deuterium isotope in R_(x) is in an amount greater than 95%of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention includealdehydes 65-358 listed in the Table A below. For each aldehyde listedin the table, the original aldehyde hydrogen (C(O)—H) has been replacedby R_(x)(C(O)—R_(x)). For example, formaldehyde-R_(x) (CHO—R_(x)) isHC(O)—R_(x).

TABLE A Ex. Name Formula 65. Formaldehyde-R_(x) CHO—R_(x) 66.2-Methyl-2-propenal-R_(x) C₄H₅O—R_(x) 67. 2-Methylpropanal-R_(x)C₄H₇O—R_(x) 68. 2-Propenal-R_(x) C₃H₃O—R_(x) 69. 2-Butenal-R_(x)C₄H₅O—R_(x) 70. 2-Methyl-2-butenal-R_(x) C₅H₇O—R_(x) 71.2-Methylenebutanal-R_(x) C₅H₇O—R_(x) 72. 3-Methyl-2-butenal-R_(x)C₅H₇O—R_(x) 73. 3-Methyl-3-butenal-R_(x) C₅H₇O—R_(x) 74.3-Methylbutanal-R_(x) C₅H₉O—R_(x) 75. (E)-2-Pentenal-R_(x) C₅H₇O—R_(x)76. 2-Methylenepentanal-R_(x) C₆H₉O—R_(x) 77. 2-Pentenal-R_(x)C₅H₇O—R_(x) 78. 3-Methyl-1-(vinyloxy)-butane-R_(x) C₇H₁₃O—R_(x) 79.4-Methylpentanal-R_(x) C₆H₁₁O—R_(x) 80. Furan-2-carbaldehyde-R_(x)C₅H₃O₂—R_(x) 81. (E)-2-Hexenal-R_(x) C₆H₉O—R_(x) 82.(E)-4-oxo-2-Hexenal-R_(x) C₆H₇O₂—R_(x) 83.(E,E)-2,4-Dimethyl-2,4-hexadienal-R_(x) C₈H₁₁O—R_(x) 84.(E,E)-2,4-Hexadienal-R_(x) C₆H₇O—R_(x) 85. (Z)-2-Hexenal-R_(x)C₆H₉O—R_(x) 86. (Z)-3-Hexenal-R_(x) C₆H₉O—R_(x) 87.(Z)-4-oxo-2-Hexenal-R_(x) C₆H₇O₂—R_(x) 88. 1-Hexenal-R_(x) C₆H₉O—R_(x)89. 2,3-Dihydroxybenzaldehyde-R_(x) C₇H₅O₃—R_(x) 90. 2-Hexenal-RR_(x)C₆H₉O—R_(x) 91. 3-((E)-2-Hexenoxy)-hexanal-R_(x) C₁₂H₂₁O₂—R_(x) 92.3,5-Dimethylhexanal-R_(x) C₈H₁₅O—R_(x) 93. 3-Ethoxyhexanal-R_(x)C₈H₁₅O₂—R_(x) 94. 3-Hydroxybenzaldehyde-R_(x) C₇H₅O₂—R_(x) 95.3-Hydroxyhexanal-R_(x) C₆H₁₁O₂—R_(x) 96.4-Hydroxy-3,5-dimethoxybenzaldehyde-R_(x) C₉H₉O₄—R_(x) 97.4-Hydroxybenzaldehyde-R_(x) C₇H₅O₂—R_(x) 98. 5-Methylhexanal-R_(x)C₇H₁₃O—R_(x) 99. Hexanal-R_(x) C₆H₁₁O—R_(x) 100.(1R,2S,5S)-Iridodial-R_(x) C₁₀H₁₅O₂—R_(x) 101.(1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R_(x)C₁₀H₁₃O—R_(x) 102.(1S,2R,3S)-2-(1-Formylvinyl)-5-methylcyclopentanecarbaldehyde-C₁₀H₁₃O₂—R_(x) R_(x) 103.(3S,8R)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x)carbaldehyde-R_(x) 104.(3S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x)carbaldehyde-R_(x) 105.(5S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x)carbaldehyde-R_(x) 106.(E)-2-(2-Hydroxyethyl)-6-methyl-2,5-heptadienal-R_(x) C₁₀H₁₅O₂—R_(x)107. (E)-2-(2-Hydroxyethylidene)-6-methyl-5-heptenal-R_(x)C₁₀H₁₅O₂—R_(x) 108. (E)-2-Heptenal-R_(x) C₇H₁₁O—R_(x) 109.(E)-2-Isopropyl-5-methyl-2-hexenal-R_(x) C₁₀H₁₇O—R_(x) 110.(E,Z)-2,4-Heptadienal-R_(x) C₇H₉O—R_(x) 111.(R)-2-((1R,2R,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_(x)C₁₁H₁₉O₂—R_(x) 112.(R)-2-((1S,2S,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_(x)C₁₁H₁₉O₂—R_(x) 113. (R)-2,6-Dimethyl-5-heptenal-R_(x) C₉H₁₅O—R_(x) 114.(R)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R_(x)C₈H₈NO₂—R_(x) 115.(S)-4-(Prop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R_(x) C₁₀H₁₃O—R_(x)116. (S)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R_(x)C₈H₈NO₂—R_(x) 117. (Z)-2-Isopropyl-5-methyl-2-hexenal-R_(x)C₁₀H₁₇O—R_(x) 118. 1-Formyl-6,7-dihydro-5H-pyrrolizine-R_(x)C₈H₈NO—R_(x) 119. 1-Formyl-7-hydroxy-6,7-dihydro-5H-pyrrolizine-R_(x)C₉H₁₂NO₂—R_(x) 120. 2-(3-Methylcyclopentyl)-propanal-R_(x) C₉H₁₅O—R_(x)121. 2,6-Dimethyl-5-heptenal-R_(x) C₉H₁₅O—R_(x) 122.2-Acetyl-5-methylcyclopentanecarbaldehyde-R_(x) C₉H₁₃O₂—R_(x) 123.2-Methoxybenzaldehyde-R_(x) C₈H₇O₂—R_(x) 124.2-Methyl-1-cyclopentenecarboxaldehyde-R_(x) C₇H₉O—R_(x) 125.3,3-Dimethyl-5-oxo-7-oxabicyclo[4.1.0]heptane-1-carbaldehyde-R_(x)C₉H₁₁O₃—R_(x) 126. 3-Hydroxybenzene-1,2-dicarbaldehyde-R_(x)C₈H₅O₃—R_(x) 127. 3-Methylbenzaldehyde-R_(x) C₈H₇O—R_(x) 128.4-(Heptyloxy)-butanal-R_(x) C₁₁H₂₁O₂—R_(x) 129.4-Methoxybenzaldehyde-R_(x) C₈H₇O₂—R_(x) 130.6,7-Dihydro-5H-pyrrolizine-1-carboxaldehyde-R_(x) C₈H₈NO—R_(x) 131.6,7-Dihydro-7-oxo-5H-pyrrolizine-1-carbaldehyde-R_(x) C₈H₆NO₂—R_(x) 132.6-Methylheptanal-Rx C₈H₁₅O—R_(x) 133.7-Hydroxy-6,7-dihydro-5H-pyrrolizin-1-carboxaldehyde-R_(x) C₈H₈NO₂—R_(x)134. Benzaldehyde-R_(x) C₇H₅O—R_(x) 135. Cyclohexanedial-R_(x)C₈H₁₁O₂—R_(x) 136. Heptanal-R_(x) C₇H₁₃O—R_(x) 137. Plagiodial-R_(x)C₁₀H₁₃O₂—R_(x) 138.(1R,2S)-cis-2-Isopropenyl-1-methylcyclobutaneethanal-R_(x) C₁₀H₁₅O—R_(x)139. (1R,2S,5R,8R)-Iridodial-R_(x) C₁₀H₁₅O₂—R_(x) 140.(4S)-(3-Oxoprop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R_(x)C₁₀H₁₁O₂—R_(x) 141.(E)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_(x) C₁₀H₁₅O—R_(x)142. (E)-2-(4-Methyl-3-pentenyl)-butenedial-R_(x) C₁₀H₁₃O₂—R_(x) 143.(E)-2-(4-Methyl-3-pentenylidene)-butanedial-R_(x) C₁₀H₁₃O₂—R_(x) 144.(E)-2,7-Octadienal-R_(x) C₈H₁₁O—R_(x) 145.(E)-2-Methyl-5-(3-furyl)-2-pentenal-R_(x) C₁₀H₁₁O₂—R_(x) 146.(E)-2-Octenal-R_(x) C₈H₁₃O—R_(x) 147.(E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 148.(E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 149.(E)-4-oxo-2-Octenal-R_(x) C₈H₁₁O₂—R_(x) 150.(E)-7-Methyl-2-octenal-R_(x) C₉H₁₅O—R_(x) 151.(E,E)-2,4-Octadienal-R_(x) C₈H₁₁O—R_(x) 152.(E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadienal-R_(x) C₁₀H₁₅O₂—R_(x) 153.(E,E)-2,6-Octadienal-R_(x) C₈H₁₁O—R_(x) 154.(E,E)-2,6-Octadienedial-R_(x) C₈H₉O₂—R_(x) 155.(E,Z)-2,4-Octadienal-R_(x) C₈H₁₁O—R_(x) 156. (E,Z)-2,6-Octadienal-R_(x)C₈H₁₁O—R_(x) 157. (Z)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_(x)C₁₀H₁₅O—R_(x) 158. (Z)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x)159. (Z,E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 160.1-Octenal-R_(x) C₈H₁₃O—R_(x) 161.2-(1-Formylvinyl)-5-methylcyclopentanecarbaldehyde-R_(x) C₁₀H₁₃O₂—R_(x)162. 2,6,6-Trimethyl-1-cyclohexene-1-carbaldehyde-R_(x) C₁₀H₁₅O—R_(x)163. 2-Ethyloctanal-R_(x) C₁₀H₁₉O—R_(x) 164.2-Hydroxy-6-methylbenzaldehyde-R_(x) C₈H₇O₂—R_(x) 165. 2-Methylbenzaldehyde-R_(x) C₈H₇O—R_(x) 166. 2-Octenal-R_(x) C₈H₁₃O—R_(x) 167.2-Phenylpropenal-R_(x) C₉H₇O—R_(x) 168. 3,7-Dimethyl-6-octenal-R_(x)C₁₀H₁₇O—R_(x) 169. 3-Ethoxy-4-hydroxybenzaldehyde-R_(x) C₉H₉O₃—R_(x)170. 3-Ethyl benzaldehyde-R_(x) C₉H₉O—R_(x) 171. 3-Isopropyl-6-methylbenzaldehyde-R_(x) C₁₁H₁₃O—R_(x) 172. 3-Octenal-R_(x) C₈H₁₃O—R_(x) 173.3-oxo-4-Isopropylidene-1-cyclohexene-1-carboxyaldehyde-R_(x)C₁₀H₁₁O₂—R_(x) 174. 4-Hydroxy-2-methyl benzaldehyde-R_(x) C₈H₇O₂—R_(x)175. 4-Hydroxy-3-methoxybenzaldehyde-R_(x) C₈H₇O₃—R_(x) 176.4-Isopropenyl-1-cyclohexene-1-carbaldehyde-R_(x) C₁₀H₁₃O—R_(x) 177.4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R_(x) C₁₀H₁₁O₂—R_(x)178. 4-oxo-Octenal-R_(x) C₈H₁₁1O₂—R_(x) 179.4S-4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R_(x)C₁₀H₁₁O₂—R_(x) 180.6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R_(x) C₁₀H₁₃O—R_(x)181. 7-Methyloctanal-R_(x) C₉H₁₇O—R_(x) 182. Anisomorphal-R_(x)C₁₀H₁₃O₂—R_(x) 183. cis-2-Isopropenyl-1-methylcyclobutaneethanal-R_(x)C₁₀H₁₅O—R_(x) 184. Octanal-R_(x) C₈H₁₅O—R_(x) 185. Peruphasmal-R_(x)C₁₀H₁₃O₂—R_(x) 186. (E)-4,8-Nonadienal-R_(x) C₉H₁₃O—R_(x) 187.(E)-8-Methyl-2-nonenal-R_(x) C₁₀H₁₇O—R_(x) 188.(E,E)-2,4-Nonadienal-R_(x) C₉H₁₃O—R_(x) 189.(E,E,E)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 190.(E,E,Z)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 191.(E,Z)-2,6-Nonadienal-R_(x) C₉F1₁₃O—R_(x) 192.(E,Z,Z)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 193. (Z)-3-Nonenal-R_(x)C₉H₁₅O—R_(x) 194. (Z)-4,8-Nonadienal-R_(x) C₉H₁₃O—R_(x) 195.(Z)-4-Nonenal-R_(x) C₉H₁₅O—R_(x) 196. (Z)-8-Methyl-2-nonenal-R_(x)C₁₀H₁₇O—R_(x) 197. 2-Phenyl-2-butenal-R_(x) C₁₀H₉O—R_(x) 198.3-(4-Methoxyphenyl)-2-propenal-R_(x) C₁₀H₉O₂—R_(x) 199.3-Phenyl-2-propenal-R_(x) C₉H₇O—R_(x) 200. 3-Phenylpropanal-R_(x)C₉H₉O—R_(x) 201. 6-Ethyl benzaldehyde-R_(x) C₉H₉O—R_(x) 202.8-Methylnonanal-R_(x) C₁₀H₁₉O—R_(x) 203. 9-Acetyloxynonanal-R_(x)C₁₁H₁₉O₃—R_(x) 204. Nonanal-R_(x) C₉H₁₇O—R_(x) 205.(E)-2,9-Decadienal-R_(x) C₁₀H₁₅O—R_(x) 206. (E)-2-Decenal-R_(x)C₁₀H₁₇O—R_(x) 207. (E)-4-oxo-2-Decenal-R_(x) C₁₀H₁₅O₂—R_(x) 208.(E)-8-Hydroxy-4,8-dimethyl-4,9-decadienal-R_(x) C₁₂H₁₉O₂—R_(x) 209.(E)-9-Methyl-2-decenal-R_(x) C₁₁H₁₉O—R_(x) 210.(E,E)-2,4-Decadienal-R_(x) C₁₀H₁₅O—R_(x) 211. (E,Z)-2,4-Decadienal-R_(x)C₁₀H₁₅O—R_(x) 212. (Z)-4-Decenal-R_(x) C₁₀H₁₇O—R_(x) 213.(Z)-5-Decenal-R_(x) C₁₀H₁₇O—R_(x) 214. (Z)-9-Methyl-2-decenal-R_(x)C₁₁H₁₉O—R_(x) 215. 1-Decenal-R_(x) C₁₀H₁₇O—R_(x) 216. 2-Decenal-R_(x)C₁₀H₁₇O—R_(x) 217. 2-Ethyldecanal-R_(x) C₁₂H₂₃O—R_(x) 218. Decanal-R_(x)C₁₀H₁₉O—R_(x) 219. (5E)-2,6,10-Trimethylundeca-5,9-dienal-R_(x)C₁₄H₂₃O—R_(x) 220. (E)-2-Undecenal-R_(x) C₁₁H₁₉O—R_(x) 221.(E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal-R_(x) C₁₅H₂₅O—R_(x) 222.10-Undecenal-R_(x) C₁₁H₁₉O—R_(x) 223. 2-Butyl-2-octenal-R_(x)C₁₂H₂₁O—R_(x) 224. 5-Methyl-2-phenyl-2-hexenal-R_(x) C₁₃H₁₅O—R_(x) 225.8-Isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-2-C₁₅H₂₃O—R_(x) carbaldehyde-R_(x) 226. syn-4,6-Dimethylundecanal-R_(x)C₁₃H₂₅O—R_(x) 227. Undecanal-R_(x) C₁₁H₂₁O—R_(x) 228.(3R,5R,9R)-3,5,9-Trimethyldodecanal-R_(x) C₁₅H₂₉O—R_(x) 229.(3S,6E)-7-Ethyl-3,11-dimethyldodeca-6,10-dienal-R_(x) C₁₆H₂₇O—R_(x) 230.(9R)-3,5,9-Trimethyldodecanal-R_(x) C₁₅H₂₉O—R_(x) 231.(E)-10-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 232. (E)-2-Dodecenal-R_(x)C₁₂H₂₁O—R_(x) 233. (E)-3,7,11-Trimethyl-6,10-dodecadienal-R_(x)C₁₅H₂₅O—R_(x) 234. (E)-6-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 235.(E)-7-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 236. (E)-8-Dodecenal-R_(x)C₁₂H₂₁O—R_(x) 237. (E)-9,11-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 238.(E)-9-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 239.(E,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R_(x) C₁₅H₂₃O—R_(x) 240.(E,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_(x) C₁₆H₂₅O—R_(x)241. (E,E)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 242.(E,E,E)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R_(x) C₁₄H₁₇O₃—R_(x)243. (E,E,Z)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R_(x)C₁₄H₁₇O₃—R_(x) 244. (E,Z)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 245.(E,Z)-7,9-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 246.(E,Z)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 247.(S,E)-3,7,11-Trimethyl-6,10-dodecadienal-R_(x) C₁₅H₂₅O—R_(x) 248.(Z)-2-Methyl-5-((1R,5R,6S)-2,6-dimethylbicyclo[3.1.1]hept-2-en-C₁₅H₂₁O—R_(x) 6-yl)-pent-2-enal-R_(x) 249. (Z)-5-Dodecenal-R_(x)C₁₂H₂₁O—R_(x) 250. (Z)-7-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 251.(Z)-9,11-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 252. (Z)-9-Dodecenal-R_(x)C₁₂H₂₁O—R_(x) 253. (Z,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R_(x)C₁₅H₂₃O—R_(x) 254. (Z,E)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 255.(Z,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_(x) C₁₆H₂₅O—R_(x)256. (Z,E)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 257.(Z,Z)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 258. 2-Ethyldodecanal-R_(x)C₁₄H₂₇O—R_(x) 259. 3,7,11-Trimethyl-(E)-6,10-dodecadienal-R_(x)C₁₅H₂₅O—R_(x) 260. Dodecanal-R_(x) C₁₂H₂₃O—R_(x) 261.syn-4,6-Dimethyldodecanal-R_(x) C₁₄H₂₇O—R_(x) 262.(3S,4R,6E,10Z)-3,4,7,11-Tetramethyl-6,10-tridecadienal-R_(x)C₁₇H₂₉O—R_(x) 263. (Z)-4-Tridecenal-R_(x) C₁₃H₂₃O—R_(x) 264.13-Acetyloxytridecanal-R_(x) C₁₅H₂₇O₃—R_(x) 265. Tridecanal-R_(x)C₁₃H₂₅O—R_(x) 266. (E)-11,13-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 267.(E,E)-8,10-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 268.(E,Z)-4,9-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 269.(Z)-11,13-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 270.(Z)-5-Tetradecenal-R_(x) C₁₄H₂₅O—R_(x) 271. (Z)-7-Tetradecenal-R_(x)C₁₄H₂₅O—R_(x) 272. (Z)-9,13-Tetradecadien-11-ynal-R_(x) C₁₄H₁₉O—R_(x)273. (Z,E)-9,12-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 274.(Z,Z)-8,10-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 275.(Z,Z)-9,11-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 276.10,12-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 277. 2-Ethyltetradecanal-R_(x)C₁₆H₃₁O—R_(x) 278. 3-oxo-13-Tetradecenal-R_(x) C₁₄H₂₃O₂—R_(x) 279.3-oxo-Tetradecanal-R_(x) C₁₄H₂₅O₂—R_(x) 280. 5,8-Tetradecadienal-R_(x)C₁₄H₂₃O—R_(x) 281. 5-Tetradecenal-R_(x) C₁₄H₂₅O—R_(x) 282.(E)-5,9-Dimethyl-2-(6-methylhept-5-en-2-yl)-deca-4,8-dienal-R_(x)C₂₀H₃₃O—R_(x) 283. (E,Z)-9,11-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 284.(Z)-10-Pentadecenal-R_(x) C₁₅H₂₇O—R_(x) 285.(Z)-6,14-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 286.(Z,Z)-9,11-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 287.2-Hexyl-2-decenal-R_(x) C₁₆H₂₉O—R_(x) 288. Pentadecanal-R_(x)C₁₅H₂₉O—R_(x) 289. (1R)-Pimaral-R_(x) C₂₀H₂₉O—R_(x) 290.(E)-10-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 291. (E)-11-Hexadecenal-R_(x)C₁₆H₂₉O—R_(x) 292. (E,E)-10,14-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 293.(E,E)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 294.(E,E)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 295.(E,E,E)-10,12,14-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x) 296.(E,E,E)-3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenal-R_(x)C₂₀H₃₁O—R_(x) 297. (E,E,Z)-10,12,14-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x)298. (E,E,Z)-4,6,11-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x) 299.(E,E,Z,Z)-4,6,11,13-Hexadecatetraenal-R_(x) C₁₆H₂₃O—R_(x) 300.(E,Z)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 301.(E,Z)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 302.(E,Z)-4,6-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 303.(E,Z)-6,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 304.(E,Z)-8,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 305.(E,Z)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 306.(Z)-10-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 307. (Z)-12-Hexadecenal-R_(x)C₁₆H₂₉O—R_(x) 308. (Z)-13-Hexadecen-11-ynal-R_(x) C₁₆H₂₅O—R_(x) 309.(Z)-3-oxo-9-Hexadecenal-R_(x) C₁₆H₂₇O₂—R_(x) 310.(Z,E)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 311.(Z,E)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 312.(Z,E)-7,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 313.(Z,E)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 314.(Z,Z)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 315.(Z,Z)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 316.(Z,Z)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 317. 11-Hexadecynal-R_(x)C₁₆H₂₇O—R_(x) 318. 2-Methylhexadecanal-R_(x) C₁₇H₃₃O—R_(x) 319.7-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 320. 9-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x)321. (Z)-9-Heptadecenal-R_(x) C₁₇H₃₁O—R_(x) 322. 1-Heptadecenal-R_(x)C₁₇H₃₁O—R_(x) 323. 2-Heptadecenal-R_(x) C₁₇H₃₁O—R_(x) 324.Heptadecanal-R_(x) C₁₇H₃₃O—R_(x) 325. (E)-11-Octadecenal-R_(x)C₁₈H₃₃O—R_(x) 326. (E)-13-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 327.(E)-14-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 328. (E)-2-Octadecenal-R_(x)C₁₈H₃₃O—R_(x) 329. (E,E)-11,14-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 330.(E,Z)-2,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 331.(E,Z)-3,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 332.(Z)-11-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 333. (Z)-13-Octadecenal-R_(x)C₁₈H₃₃O—R_(x) 334. (Z)-9-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 335.(Z,Z)-11,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 336.(Z,Z)-13,15-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 337.(Z,Z)-3,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 338.(Z,Z)-9,12-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 339.(Z,Z,Z)-9,12,15-Octadecatrienl-R_(x) C₁₈H₂₉O—R_(x) 340.1-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 341. 9-Octadecenal-R_(x) C₁₈H₃₃O—R_(x)342. Octadecanal-R_(x) C₁₈H₃₅O—R_(x) 343. (Z)-10-Nonadecenal-R_(x)C₁₉H₃₅O—R_(x) 344. (Z)-9-Nonadecenal-R_(x) C₁₉H₃₅O—R_(x) 345.(Z)-11-Eicosenal-R_(x) C₂₀H₃₇O—R_(x) 346.12-Deacetoxy-12-oxo-scalaradial-R_(x) C₂₅H₃₅O₃—R_(x) 347.1-Eicosenal-R_(x) C₂₀H₃₇O—R_(x) 348. Deacetylscalaraial-R_(x)C₂₅H₃₇O₃—R_(x) 349. Eicosanal-R_(x) C₂₀H₃₉O—R_(x) 350. Scalaradial-R_(x)C₂₇H₃₉O₄—R_(x) 351. Docosanal-R_(x) C₂₂H₄₃O—R_(x) 352.Tetracosanal-R_(x) C₂₄H₄₇O—R_(x) 353. Pentacosanal-R_(x) C₂₅H₄₉O—R_(x)354. Hexacosanal-R_(x) C₂₆H₅₁O—R_(x) 355. Heptacosanal-R_(x)C₂₇H₅₃O—R_(x) 356. Octacosanal-R_(x) C₂₈H₅₅O—R_(x) 357.Triacontanal-R_(x) C₃₀H₅₉O—R_(x) 358. Dotriacontanal-R_(x) C₃₂H₆₃O—R_(x)

Additional deuterium-enriched aldehydes of the present invention includealdehydes 65-358 listed in the Tables B-L below.

Table B: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 2% of the hydrogen atoms presentin R_(x).

Table C: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 10% of the hydrogen atoms presentin R_(x).

Table D: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 20% of the hydrogen atoms presentin R_(x).

Table E: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 30% of the hydrogen atoms presentin R_(x).

Table F: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 40% of the hydrogen atoms presentin R_(x).

Table G: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 50% of the hydrogen atoms presentin R_(x).

Table H: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 60% of the hydrogen atoms presentin R_(x).

Table I: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 70% of the hydrogen atoms presentin R_(x).

Table J: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 80% of the hydrogen atoms presentin R_(x).

Table K: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 90% of the hydrogen atoms presentin R_(x).

Table L: Examples 64-358 of Table A, except that the deuterium isotopein R_(x) is in an amount greater than 95% of the hydrogen atoms presentin R_(x).

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table A.

Reference to “compositions comprising compounds 65-358” meanscompositions comprising at least 6×10¹⁸ molecules of at least one ofaldehydes 65-358, typically at least 6×10¹⁹ molecules, and may, forexample, comprise at least 6×10²⁰ molecules, 6×10²¹ molecules, 6×10²²molecules, or 6×10²³ molecules. R_(x) is hydrogen, wherein the deuteriumisotope is in an amount greater than 0.10 percent of the R_(x) hydrogenatoms. In certain cases, the deuterium isotope comprises greater than 1%of the hydrogen atoms, or even greater than 2%, 5%, 10%, 20%, 30%, 40%,50%, 60%, 70%, 80%, 90%, or 95% of the hydrogen atoms.

In another aspect, reference to “compositions comprising compounds65-358” means compositions comprising at least 0.1 mole of at least oneof aldehydes 65-358. Compositions of the invention may, for example,comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, to 20 moles of at leastone of compounds 65-358.

In another aspect, reference to “compositions comprising compounds65-358” means compositions comprising at least 1 gram of at least one ofaldehydes 65-358. Compositions of the invention may, for example,comprise at least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of atleast one of compounds 65-358.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table B.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table C.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table D.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table E.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table F.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table G.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table H.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table I.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table J.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table K.

In another aspect, the present invention provides a composition,comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358of Table L.

Compounds of the present invention are more stable to autoxidation thanthe corresponding aldehydes where the hydrogen atom attached to thecarbonyl moiety (i.e., H—C(O)) is not enriched in the deuterium isotope.For instance, where the deuterium isotope comprises greater than 90percent of the subject hydrogen atoms, the rate of autoxidation—i.e.,conversion of the aldehyde to its corresponding carboxylic acid throughoxidation by atmospheric oxidation in the absence of an oxidationcatalyst (e.g., metal or transition metal-based catalyst)—is reduced byat least 10 percent (e.g., if 10.0 percent of the aldehyde withoutdeuterium enrichment experiences autoxidation, less than 9.0 percent ofthe aldehyde with deuterium enrichment experiences autoxidation underthe same conditions). In certain cases, the rate is reduced by at least20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent,80 percent or 90 percent.

Compounds 1-358 can be synthesized using any appropriate method.Examples of such methods include: reduction of the corresponding acidhalide with deuterium gas (see U.S. Pat. No. 5,149,820); reduction ofthe corresponding tertiary amide using Cp₂Zr(D)Cl (see Georg et al. Tet.Lett. 2004; 45: 2787-2789); and, reduction of the corresponding esterusing LiAlD₄ to produce an alcohol and subsequent oxidation (see Kim etal., J. Label Compd Radiopharm 2004; 47: 921-934) (or just oxidation ofa corresponding alcohol);

Alternatively, an additional method includes reduction of theun-enriched aldehyde with NaBD₄ or NaCNBD₃ followed by re-oxidation withpyridinium chlorochromate or another suitable oxidant, in which thedeuterium enrichment of the aldehyde is a result of the isotope effect.

In another aspect, the present invention provides compositionscomprising one or more of aldehydes 1-64 and an organic solvent (e.g.,an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g.,dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, theorganic solvent is ethyl alcohol. Examples of the concentration of theethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and70-96 weight percent.

In another aspect, the present invention provides compositionscomprising one or more of aldehydes 65-358 and an organic solvent (e.g.,an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g.,dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, theorganic solvent is ethyl alcohol. Examples of the concentration of theethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and70-96 weight percent.

In another aspect, the compositions of the present invention comprise anadditional ingredient. Examples of additional ingredients include:dipropylene glycol; isopropyl myristate; oils (e.g., coconut oil); andliquid waxes (e.g., jojoba oil).

The compositions discussed herein also can be used, for example, in aperfume. Reference to “perfume” means a mixture comprising fragrantcompounds and solvents used to give the human body, animals, objects andliving spaces a pleasant scent.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects (e.g., attracting or inhibitinginsect species), comprising: a deuterium-enriched aldehyde selected fromstructures 1-64, wherein the aldehyde is a pheromone and an optionaladditional component or components suitable for the composition (e.g., apesticide, dispensing material or device, solvent, adhesive capable oftrapping the insect, etc.).

In another aspect, the present invention provides novel compositions formodulating the behavior of insects (e.g., attracting or inhibitinginsect species), comprising: a deuterium-enriched aldehyde selected fromstructures 65-358, wherein the aldehyde is a pheromone and an optionaladditional component or components suitable for the composition (e.g., apesticide, dispensing material or device, solvent, adhesive capable oftrapping the insect, etc.).

In another aspect, the composition comprises a pheromone blend.

A pheromone blend, comprises: at least one pheromone aldehyde selectedfrom the deuterium-enriched aldehydes of the present invention and atleast one additional pheromone that is either an un-enriched aldehyde ora different pheromone aldehyde selected from the deuterium-enrichedaldehydes of the present invention.

In another aspect, the present invention provides novel methods formodulating the behavior of insects (e.g., attracting insect species orinhibiting the mating or aggregation of insect species), comprising:

-   -   a. applying a deuterium-enriched aldehyde pheromone of the        present invention, or a composition comprising a        deuterium-enriched aldehyde pheromone of the present invention        and a optionally a solvent or other additional component        suitable for the composition, to a surface of an object (e.g., a        lure within a trap wherein the insect enters but cannot leave, a        lure or trap wherein the insect sticks to a surface of the trap,        or a lure or trap containing a chemical capable of killing the        insect); and,    -   b. placing the object in a location where one desires either to        attract insect species or inhibiting the mating or aggregation        of insect species.

In another aspect, a pheromone blend is applied (either neat or as apart of a composition of the present invention).

In another aspect, two or more deuterium-enriched aldehyde pheromones ofthe present invention are applied (either neat or as a part of acomposition of the present invention).

Alternatively, the method comprises: distributing a compositioncomprising a deuterium-enriched aldehyde pheromone of the presentinvention into an area (e.g., by aerial spraying over crops), into astored product (e.g., traps or disruptant dispensers in grain crops),onto vegetation (e.g., by manual application of dollops of an emulsion(e.g., SPLAT® type formulation) onto plants, vines, leaves, or shoots),or by applying by aerial dissemination or manual placement a compositionof pheromone-impregnated chips, pheromone containing polymer hollowfibers, or pheromone containing rubber septa, in order to modulate thebehavior of insects by disruption of mating behavior. More than onecomposition or method may be combined to achieve the desired reductionof crop damage.

In another aspect, a pheromone blend is present in the distributedcomposition.

In another aspect, two or more deuterium-enriched aldehyde pheromones ofthe present invention are present in the distributed composition.

In another aspect, the deuterium-enriched aldehyde pheromone of thepresent invention is distributed impregnated on a chip, in a polymerhollow fiber, or adsorbed within a rubber septum.

In another aspect, a pheromone blend is distributed impregnated on achip, in a polymer hollow fiber, or adsorbed within a rubber septum.

In another aspect, two or more deuterium-enriched aldehyde pheromones ofthe present invention are distributed impregnated on a chip, in apolymer hollow fiber, or adsorbed within a rubber septum.

The modulation of insect behavior can comprise attraction to an aldehydepheromone trap, or alternatively, disruption of mate-finding and matingbehavior. A benefit of such insect behavior modulation can be diminishedcrop damage, such as reducing damage to fruits, nuts, seeds, grains,grapes, leaves, shoots, bark, grain, or other valuable crops by reducinginsect damage to said crop, whether in the field or in storage afterharvesting said valuable crop.

In another aspect, the modulating composition of the present invention,comprises: a deuterium-enriched aldehyde pheromone of the presentinvention formulated to be used in an attractant trap (an attractantcomposition).

In another aspect, the modulating composition of the present invention,comprises: a pheromone blend formulated to be used in an attractant trap(an attractant composition).

In another aspect, two or more deuterium-enriched aldehyde pheromones ofthe present invention are present in the modulating composition.

In another aspect, the present invention provides a method of using anattractant composition in an attractant trap.

In another aspect, the present invention provides a method of using adeuterium-enriched aldehyde pheromone as a component of a composition toattract, trap, or monitor adult insects in a stored product with thegoal of minimizing crop product infestation and loss. In another aspect,a pheromone blend is in the composition. In another aspect, two or moredeuterium-enriched aldehyde pheromones of the present invention arepresent in the composition.

In another aspect, the modulating composition of the present invention,comprises a deuterium-enriched aldehyde pheromone of the presentinvention formulated to be used as a mating disruptant (a disruptantcomposition). A disruptant composition is typically dispersed throughoutpart or all of an area to be protected.

In another aspect, a pheromone blend is present in the disruptantcomposition.

In another aspect, two or more deuterium-enriched aldehyde pheromones ofthe present invention are present in the disruptant composition.

In another aspect, the present invention provides a method of using adisruptant composition in an area to be protected (e.g., a crop field).It will be understood by those skilled in the art that disruption ofmating by adult insects will reduce the population of offspring.Frequently it is the offspring, or larvae, of the species that areresponsible for damage to the field crop or harvested crop product. Askilled person will understand that disruption of mating may be anindirect method of reducing damage to field crops or harvested cropproducts by larval forms of the insects that feed on the crop or cropproduct.

In another aspect, the disruptant composition is made using an oil/wateremulsion preparation to deposit the disruptant onto a carrier. Examplesof carriers include a polymeric hollow loop, a rubber (e.g., septum) orpolymeric carrier, and impregnable chips.

Examples of types of attractant and/or disruptant formulations include:microencapsulation, hollow tube dispensers, bait stations, oil-wateremulsions, and other volatile deuterium-enriched aldehyde dispensers.

Microencapsulation refers to encapsulating at least onedeuterium-enriched aldehyde pheromone of the present invention in apolymer. The polymer is selected to delay the release of the pheromonefor at least a few days. The microencapsulated pheromone(s) can beapplied by spraying.

Examples of hollow tube dispensers include plastic twist-tie typedispensers, plastic hollow fibers, and plastic hollow microfibers. Thesetypes of dispensers are filled with at least one disruptant or adisruptant composition of the present invention and then distributedthroughout the area to be protected.

Bait stations are stationary devices that are typically used to attractand kill Examples include platforms comprising at least pheromonealdehyde of the present invention and a glue board (or some othermechanism capable of trapping the attracted insect). Instead of or inaddition to glue, the station can contain a pesticide that negativelyaffects the insect (e.g., reduces its ability to mate or reproduce).

Dispensers or high-emission dispensers are devices that either passivelyor actively release a pheromone aldehyde of the present invention.Examples of passive release include pheromone sachets or an emulsion(e.g., a SPLAT® (Specialized Lure And Pheromone Technology)formulation). Active dispensers may release bursts of at least onepheromone aldehyde of the present invention (or composition containingat least one pheromone aldehyde of the present invention) at timedintervals or by continuous release through volatilization from thedispenser.

As used herein, a pheromone is a deuterium-enriched aldehyde ofstructure 1 that has the traits of a natural pheromone, i.e., a chemicalcapable communicating with at least one insect species. Pheromones mayact as alarm signals, provide trails to food sources, attractparasitoids or other predators, and/or attract insects of the samespecies for the purpose of mating.

Unless otherwise specified, when a pheromone is recited in the presentinvention it can be a single deuterium-enriched aldehyde of structure 1or a blend of pheromones wherein at least one is a deuterium-enrichedaldehyde of structure 1. The second, third, fourth, fifth, or morepheromone can be a deuterium-enriched aldehyde of structure 1 or anon-deuterium-enriched aldehyde

In another aspect, a composition of the present invention, comprises: 2,3, 4, 5, 6, 7, 8, 9, or 10 deuterium-enriched aldehyde pheromones of thepresent invention.

In another aspect, a composition of the present invention, comprises: 2or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 3or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 4or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 5or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: atleast 1, 2, 3, 4, or 5 deuterium-enriched aldehyde pheromones of thepresent invention and at least 1, 2, 3, 4, or 5 un-enriched un-enrichedpheromones.

In another aspect, a composition of the present invention, comprises: atleast 1 deuterium-enriched aldehyde pheromone of the present inventionand at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: atleast 2 deuterium-enriched aldehyde pheromones of the present inventionand at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: atleast 1 deuterium-enriched aldehyde pheromones of the present inventionand at least 2 un-enriched pheromones.

In another aspect, a composition of the present invention, comprises: atleast 3 deuterium-enriched aldehyde pheromones of the present inventionand at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: atleast 3 deuterium-enriched aldehyde pheromones of the present inventionand at least 2 un-enriched pheromones.

In another aspect, a composition of the present invention, comprises: atleast 3 deuterium-enriched aldehyde pheromones of the present inventionand at least 3 un-enriched pheromones.

Examples of insects for which a deuterium-enriched pheromone (orpheromones) can be prepared include: corn earworm (Heliothis(Helicoverpa) zea), tobacco budworm (Heliothis virescens), cottonbollworm (Heliothis (Helicoverpa) armigera), horse chestnut leaf miner(Cameraria orhidella), eastern spruce budworm (Choristoneurafumiferana), rice borer (Chilo suppressalis), grain weevils (Trogodermaspp.), grain/flower weevils (Tribolium spp.), cotton boll weevil(Anthonomus grandis), citrus leaf miner (Phyllocnistis citrella), carobmoth (Ectomyelois ceratoniae), and Asian longhorn beetle (Anoplophoraglabripennis), among many others. A complete listing of aldehydepheromones of insects and the target species using the pheromones isavailable on the Pherobase.com data base and is hereby incorporated intotality into this application(http://www.pherobase.com/database/compound/compounds-aldes.php). One ormore of the known aldehydic pheromones for these insects can be replacedby a deuterium-enriched aldehyde of the present invention.

For example, a pheromone composition for the corn earworm containingZ11-16:Ald can be replaced with compound 27 of the present invention.Representative examples of such deuterium-enriched aldehyde pheromonesinclude compounds selected from: aldehydes 8, 15, 23, 24, 27, 28, 29,30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, and 64.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is selected from: aldehydes 27, 28, and 35.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is selected from: aldehydes 27 and 28.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 36.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is selected from: aldehydes 37 and 38.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is selected from: aldehydes 27, 28, and 44.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 49.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 55.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 59.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is selected from: aldehyde 40, 60, and 61.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 62.

In another aspect, the present invention provides novel compositions formodulating the behavior of insects, comprising: at least onedeuterium-enriched aldehyde that is a pheromone, wherein thedeuterium-enriched aldehyde is: aldehyde 64.

Compounds of the present invention are also more stable to autoxidationthan their corresponding non-deuterium enriched counterparts whenincluded in compositions of the present invention. The rate of autooxidation is reduced by at least 10 percent. In certain cases, the rateis reduced by at least 20 percent, 30 percent, 40 percent, 50 percent,60 percent, 70 percent, 80 percent or 90 percent.

The skilled person will recognize that pheromones or pheromone blendsfor a given species may include non-aldehyde components, such as analkyl, alkenyl, alkynyl alcohol or an alkyl, alkenyl or alkynyl ester.When the blend for optimal attraction includes such an additionalnon-aldehyde component, the skilled person would augment thedeuterium-labeled pheromone of the present invention with the additionalattractant or disruptant compound that increases the efficacy ofmodulation of the insect behavior, e.g., mating disruption or attractionto a trap.

In Table 1 are described examples of compositions of the presentinvention:

wherein:

-   there are at least 6×10¹⁸ molecules of the aldehyde present in the    composition;-   R_(x) is hydrogen, wherein the deuterium isotope is present in an    amount greater than 0.10% of the R_(x) hydrogen atoms;-   unless otherwise defined, R₁, R₂ and R₃ are independently selected    from hydrogen, alkyl, substituted alkyl, alkenyl, substituted    alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted    heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted    heteroaryl;-   alternatively, the CR₁R₂R₃ moiety forms a group selected from: an    aryl, substituted aryl, heteroaryl, and substituted heteroaryl;-   alternatively, the CR₁R₂ moiety forms a group a group selected from:    an alkenyl and substituted alkenyl;-   alternatively, the CR₁R₂R₃ moiety forms a group a group selected    from: an alkynyl and substituted alkynyl; and,-   optionally, the aldehyde is substituted with C(O)R_(y), wherein    R_(x) is hydrogen, wherein the deuterium isotope is present in an    amount greater than 0.10% of the R_(y) hydrogen atoms.

TABLE 1 Structure Solvent Ex. # # R₁, R₂, R₃ (weight %) A. 1 As definedEthyl alcohol 70-96% by weight B. 1 one of R₁, R₂ and R₃ is alkyl Ethylalcohol 70-96% by weight C. 1 one of R₁, R₂ and R₃ is substituted alkylEthyl alcohol 70-96% by weight D. 1 one of R₁, R₂ and R₃ is alkenylEthyl alcohol 70-96% by weight E. 1 one of R₁, R₂ and R₃ is substitutedalkenyl Ethyl alcohol 70-96% by weight F. 1 one of R₁, R₂ and R₃ isalkynyl Ethyl alcohol 70-96% by weight G. 1 one of R₁, R₂ and R₃ issubstituted alkynyl Ethyl alcohol 70-96% by weight H. 1 one of R₁, R₂and R₃ is heteroalkyl Ethyl alcohol 70-96% by weight I. 1 one of R₁, R₂and R₃ is substituted heteroalkyl Ethyl alcohol 70-96% by weight J. 1one of R₁, R₂ and R₃ is aryl Ethyl alcohol 70-96% by weight K. 1 one ofR₁, R₂ and R₃ is substituted aryl Ethyl alcohol 70-96% by weight L. 1one of R₁, R₂ and R₃ is heteroaryl Ethyl alcohol 70-96% by weight M. 1one of R₁, R₂ and R₃ is substituted heteroaryl Ethyl alcohol 70-96% byweight N. 1 one of R₁, R₂ and R₃ is alkyl and another is Ethyl alcoholhydrogen 70-96% by weight O. 1 one of R₁, R₂ and R₃ is substituted alkyland Ethyl alcohol another is hydrogen 70-96% by weight P. 1 one of R₁,R₂ and R₃ is alkenyl and another is Ethyl alcohol hydrogen 70-96% byweight Q. 1 one of R₁, R₂ and R₃ is substituted alkenyl and Ethylalcohol another is hydrogen 70-96% by weight R. 1 one of R₁, R₂ and R₃is alkynyl and another is Ethyl alcohol hydrogen 70-96% by weight S. 1one of R₁, R₂ and R₃ is substituted alkynyl and Ethyl alcohol another ishydrogen 70-96% by weight T. 1 one of R₁, R₂ and R₃ is heteroalkyl andanother Ethyl alcohol is hydrogen 70-96% by weight U. 1 one of R₁, R₂and R₃ is substituted heteroalkyl Ethyl alcohol and another is hydrogen70-96% by weight V. 1 one of R₁, R₂ and R₃ is aryl and another is Ethylalcohol hydrogen 70-96% by weight W. 1 one of R₁, R₂ and R₃ issubstituted aryl and Ethyl alcohol another is hydrogen 70-96% by weightX. 1 one of R₁, R₂ and R₃ is heteroaryl and another Ethyl alcohol ishydrogen 70-96% by weight Y. 1 one of R₁, R₂ and R₃ is substitutedheteroaryl Ethyl alcohol and another is hydrogen 70-96% by weight Z. 1R₁, R₂ and R₃ is alkyl and the other two are Ethyl alcohol hydrogen70-96% by weight AA. 1 one of R₁, R₂ and R₃ is substituted alkyl andEthyl alcohol the other two are hydrogen 70-96% by weight BB. 1 one ofR₁, R₂ and R₃ is alkenyl and the other Ethyl alcohol two are hydrogen70-96% by weight CC. 1 one of R₁, R₂ and R₃ is substituted alkenyl andEthyl alcohol the other two are hydrogen 70-96% by weight DD. 1 one ofR₁, R₂ and R₃ is alkynyl and the other Ethyl alcohol two are hydrogen70-96% by weight EE. 1 one of R₁, R₂ and R₃ is substituted alkynyl andEthyl alcohol the other two are hydrogen 70-96% by weight FF. 1 one ofR₁, R₂ and R₃ is heteroalkyl and the Ethyl alcohol other two arehydrogen 70-96% by weight GG. 1 one of R₁, R₂ and R₃3 is substitutedheteroalkyl Ethyl alcohol and the other two are hydrogen 70-96% byweight HH. 1 one of R₁, R₂ and R₃ is aryl and the other two Ethylalcohol hydrogen 70-96% by weight II. 1 one of R₁, R₂ and R₃ issubstituted aryl the Ethyl alcohol other two are hydrogen 70-96% byweight JJ. 1 one of R₁, R₂ and R₃ is heteroaryl and the Ethyl alcoholother two are hydrogen 70-96% by weight KK. 1 one of R₁, R₂ and R₃ issubstituted heteroaryl Ethyl alcohol and the other two are hydrogen70-96% by weight LL. 1 CR₁R₂R₃ is aryl Ethyl alcohol 70-96% by weightMM. 1 CR₁R₂R₃ is substituted aryl Ethyl alcohol 70-96% by weight NN. 1CR₁R₂R₃ is heteroaryl Ethyl alcohol 70-96% by weight OO. 1 CR₁R₂R₃ issubstituted heteroaryl Ethyl alcohol 70-96% by weight PP. 1 CR₁R₂alkenyl and R₃ is hydrogen Ethyl alcohol 70-96% by weight QQ. 1 CR₁R₂substituted alkenyl and R₃ is hydrogen Ethyl alcohol 70-96% by weightRR. 1 CR₁R₂ alkenyl and R₃ is alkyl Ethyl alcohol 70-96% by weight SS. 1CR₁R₂ substituted alkenyl and R₃ is alkyl Ethyl alcohol 70-96% by weightTT. 1 R₁ is alkyl substituted with C(O)R_(y) Ethyl alcohol 70-96% byweight UU. 1 R₁ is alkyl substituted with C(O)R_(y) and R₂ and Ethylalcohol R₃ are hydrogens 70-96% by weight VV. 1 CR₁R₂R₃ is arylsubstituted with C(O)R_(y) Ethyl alcohol 70-96% by weight WW. 1 CR₁R₂R₃is substituted aryl substituted with Ethyl alcohol C(O)R_(y) 70-96% byweight XX. 2 — Ethyl alcohol 70-96% by weight YY. 3 — Ethyl alcohol70-96% by weight ZZ. 4 — Ethyl alcohol 70-96% by weight AAA. 5 — Ethylalcohol 70-96% by weight BBB. 6 — Ethyl alcohol 70-96% by weight CCC. 7— Ethyl alcohol 70-96% by weight DDD. 8 — Ethyl alcohol 70-96% by weightEEE. 9 — Ethyl alcohol 70-96% by weight FFF. 10 — Ethyl alcohol 70-96%by weight GGG. 11 — Ethyl alcohol 70-96% by weight HHH. 12 — Ethylalcohol 70-96% by weight III. 13 — Ethyl alcohol 70-96% by weight JJJ.14 — Ethyl alcohol 70-96% by weight KKK. 15 — Ethyl alcohol 70-96% byweight LLL. 16 — Ethyl alcohol 70-96% by weight MMM. 17 — Ethyl alcohol70-96% by weight NNN. 18 — Ethyl alcohol 70-96% by weight OOO. 19 —Ethyl alcohol 70-96% by weight PPP. 20 — Ethyl alcohol 70-96% by weightQQQ. 21 — Ethyl alcohol 70-96% by weight RRR. 22 — Ethyl alcohol 70-96%by weight SSS. 23 — Ethyl alcohol 70-96% by weight TTT. 24 — Ethylalcohol 70-96% by weight UUU. 25 — Ethyl alcohol 70-96% by weight VVV.26 — Ethyl alcohol 70-96% by weight WWW. 27 — Ethyl alcohol 70-96% byweight XXX. 28 — Ethyl alcohol 70-96% by weight YYY. 29 — Ethyl alcohol70-96% by weight ZZZ. 30 — Ethyl alcohol 70-96% by weight AAAA. 31 —Ethyl alcohol 70-96% by weight BBBB. 32 — Ethyl alcohol 70-96% by weightCCCC. 33 — Ethyl alcohol 70-96% by weight DDDD. 34 — Ethyl alcohol70-96% by weight EEEE. 35 — Ethyl alcohol 70-96% by weight FFFF. 36 —Ethyl alcohol 70-96% by weight GGGG. 37 — Ethyl alcohol 70-96% by weightHHHH. 38 — Ethyl alcohol 70-96% by weight IIII 39 — Ethyl alcohol 70-96%by weight JJJJ. 40 — Ethyl alcohol 70-96% by weight KKKK. 41 — Ethylalcohol 70-96% by weight LLLL. 42 — Ethyl alcohol 70-96% by weight MMMM.43 — Ethyl alcohol 70-96% by weight NNNN. 44 — Ethyl alcohol 70-96% byweight OOOO. 45 — Ethyl alcohol 70-96% by weight PPPP. 46 — Ethylalcohol 70-96% by weight QQQQ. 47 — Ethyl alcohol 70-96% by weight RRRR.48 — Ethyl alcohol 70-96% by weight SSSS. 49 — Ethyl alcohol 70-96% byweight TTTT. 50 — Ethyl alcohol 70-96% by weight UUUU. 51 — Ethylalcohol 70-96% by weight VVVV. 52 — Ethyl alcohol 70-96% by weight WWWW.53 — Ethyl alcohol 70-96% by weight XXXX. 54 — Ethyl alcohol 70-96% byweight YYYY. 55 — Ethyl alcohol 70-96% by weight ZZZZ. 56 — Ethylalcohol 70-96% by weight AAAAA. 57 — Ethyl alcohol 70-96% by weightBBBBB. 58 — Ethyl alcohol 70-96% by weight CCCCC. 59 — Ethyl alcohol70-96% by weight DDDDD. 60 — Ethyl alcohol 70-96% by weight EEEEE. 61 —Ethyl alcohol 70-96% by weight FFFFF. 62 — Ethyl alcohol 70-96% byweight GGGGG. 63 — Ethyl alcohol 70-96% by weight HHHHH. 64 — Ethylalcohol 70-96% by weight

Table 2: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH ofTable 1, except that the deuterium isotope in R_(x) is in an amountgreater than 2% of the hydrogen atoms present in R_(x).

Table 3: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH ofTable 1, except that the deuterium isotope in R_(x) is in an amountgreater than 10% of the hydrogen atoms present in R_(x).

Table 4: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH ofTable 1, except that the deuterium isotope in R_(x) is in an amountgreater than 50% of the hydrogen atoms present in R_(x).

Table 5: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH ofTable 1, except that the deuterium isotope in R_(x) is in an amountgreater than 90% of the hydrogen atoms present in R_(x).

In another aspect, compounds according to the present invention can beused to make resins and/or polymers. The method comprises the steps of:mixing a deuterium-enriched aldehyde selected from structures 1-64 withan aromatic compound (i.e., aryl-containing compound) or an olefiniccompound (i.e., alkenyl-containing compound) in a solvent and in thepresence of a catalyst, in such a way as to initiate a reaction betweenthe aromatic or olefinic compound and the aldehyde; and, isolating thereaction product (e.g., resin or polymer) resulting from the reaction.The catalyst may be a Bronsted acid (e.g., aqueous sulfuric orhydrochloric acid), a Lewis acid (e.g., AlCl₃), a base (e.g., KOH) or ametal (e.g., transition metal). The reaction may be carried out at roomtemperature or at elevated temperature (e.g., 50° C., 60° C., 70° C.,80° C., 90° C., 100° C., 110° C. or 120° C.). The reaction may also becarried out at atmospheric pressure or at elevated pressure (e.g., 2atm, 3 atm, 4 atm or 5 atm).

In another aspect, compounds according to the present invention can beused to make resins and/or polymers. The method comprises the steps of:mixing a deuterium-enriched aldehyde selected from structures 65-358with an aromatic compound (i.e., aryl-containing compound) or anolefinic compound (i.e., alkenyl-containing compound) in a solvent andin the presence of a catalyst, in such a way as to initiate a reactionbetween the aromatic or olefinic compound and the aldehyde; and,isolating the reaction product (e.g., resin or polymer) resulting fromthe reaction. The catalyst may be a Bronsted acid (e.g., aqueoussulfuric or hydrochloric acid), a Lewis acid (e.g., AlCl₃), a base(e.g., KOH) or a metal (e.g., transition metal). The reaction may becarried out at room temperature or at elevated temperature (e.g., 50°C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C. or 120° C.). Thereaction may also be carried out at atmospheric pressure or at elevatedpressure (e.g., 2 atm, 3 atm, 4 atm or 5 atm).

The rate of autoxidation of aldehydes in the polymerization/resinproducing reaction is reduced by at least 10 percent as compared to useof non-deuterium enriched aldehydes under the same conditions. Incertain cases, the rate is reduced by at least 20 percent, 30 percent,40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90percent.

The following general methods of making a resin and/or polymer are meantto illustrate, not limit, the present invention.

General Method 1

An aromatic compound (e.g., naphthalene, benzene, substituted benzenesuch as toluene) is heated in an acidic mixture (e.g., sulfuric acid andwater) for 6 hours at 160° C. The mixture is cooled to 100° C., and adeuterium-enriched aldehyde selected from structures 1-64 is added in anamount that is less than a molar equivalent of the aromatic compound.The resulting mixture is kept at 100° C. at a time period ranging from30 minutes to 16 hours to afford a condensation polymer.

General Method 1A

An aromatic compound (e.g., naphthalene, benzene, substituted benzenesuch as toluene) is heated in an acidic mixture (e.g., sulfuric acid andwater) for 6 hours at 160° C. The mixture is cooled to 100° C., and adeuterium-enriched aldehyde selected from structures 65-358 is added inan amount that is less than a molar equivalent of the aromatic compound.The resulting mixture is kept at 100° C. at a time period ranging from30 minutes to 16 hours to afford a condensation polymer.

General Method 2

To a mixture of a deuterium-enriched aldehydes selected from structures1-64 and an aromatic alcohol (e.g., resorcinol) at room temperature isadded an acidic solution (e.g., aqueous HCl). This affords acondensation polymer upon isolation.

General Method 2B

To a mixture of a deuterium-enriched aldehydes selected from structures65-358 and an aromatic alcohol (e.g., resorcinol) at room temperature isadded an acidic solution (e.g., aqueous HCl). This affords acondensation polymer upon isolation.

General Method 3

To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent(e.g., ether such as dioxane) is slowly added acid (e.g., sulfuricacid). A deuterium-enriched aldehyde selected from structures 1-64 isadded dropwise with stirring. The reaction mixture is heated and thecontents refluxed for 2 hours. The organic solvent and water areremoved, and the reaction mixture is cooled. Precipitation of materialprovides the condensation polymer.

General Method 3A

To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent(e.g., ether such as dioxane) is slowly added acid (e.g., sulfuricacid). A deuterium-enriched aldehyde selected from structures 65-358 isadded dropwise with stirring. The reaction mixture is heated and thecontents refluxed for 2 hours. The organic solvent and water areremoved, and the reaction mixture is cooled. Precipitation of materialprovides the condensation polymer.

General Procedure for Measurement of Aldehyde Oxidations

To a 12 mL clear, colorless, glass vial, fitted with a stir bar, wasadded the aldehyde (1 mmol), triacetin (2.0 mL), and water (0.10 mL,purified by reverse osmosis). The top of the vial was covered with atissue and the mixture was stirred vigorously at room temperature. Inthe benzaldehyde reactions, (both H and D), 4.0 μL aliquots werewithdrawn at 0, 0.5, 18, 25, 96, and 120 hour time points. These werediluted with ethanol (1.0 mL), and analyzed by HPLC. In the hexanalreactions (both H and D), 45 μL aliquots were withdrawn at 2, 4, 6, and24 hour time points. These were diluted with ethanol (1.0 mL) andanalyzed by GC.

Instruments and Conditions Used for Analysis:

High pressure liquid chromatography: Agilent XDB C18 50×4.6 mm 1.8micron column

Solvent A—Water (0.1% TFA)

Solvent B—Acetonitrile (0.07% TFA)

Gradient—5 min 95% A to 95% B then 1 minute hold. 1.5 mL/min

UV Detection (integration) @210 and 254 nm

Gas chromatography:

HP 6890GC Column=Agilent DB-5 15 m×0.25 mm capillary column.

35° C. start (2 min hold), ramping to 100° C. at 5° C. per minute

7.8 mL/min gas flow

Flame Ion Detection (integration)

Example 1

The oxidation rate of deuterium enriched benzaldehyde (i.e., >95%deuterium at the α-H, i.e., H—C(O)Ph, “benzaldehyde-D”) to benzoic acidwas compared against un-enriched benzaldehyde (i.e., naturally occurringisotopic abundance, “benzaldehyde-H”), using the above-describedprocedure. The time and amount of aldehyde remaining were plotted asshown in FIG. 4. After 24 hours, approximately 90% of benzaldehyde-Dremained (a 10% loss). In contrast, after 24 hours, approximately 30% ofbenzaldehyde-H remained (a 70% loss). The autoxidation of deuteriumenriched benzaldehyde was reduced by over 50 percent after a period ofapproximately 24 hours due to the presence of deuterium.

Example 2

The oxidation rate of deuterium enriched hexanal (i.e., >95% deuteriumat α-hydrogen i.e., H—C(O)C₅H₁₁, “hexanal-D”) to hexanoic acid wascompared against un-enriched hexanal (i.e., naturally occurring isotopicabundance, “hexanal-H”) using the above-described procedure. The timeand amount of aldehyde remaining were plotted as shown in FIG. 5. After24 hours, approximately 90% of hexanal-D remained (a 10% loss). Incontrast, after 24 hours, approximately 30% of hexanal-H remained (a 70%loss). The autoxidation of deuterium-enriched hexanal was reduced byabout 50 percent after a period of approximately 24 hours.

Numerous modifications and variations of the present invention arepossible in light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims, the inventionmay be practiced otherwise that as specifically described herein.

What is claimed is:
 1. An insect behavior modulating composition formodulating the behavior of the citrus leafminer, Phyllocnistis citrella,comprising: a deuterium-enriched aldehyde of formula 61:

wherein: there are at least 6×10¹⁸ molecules of the aldehyde in thecomposition; R_(x) is hydrogen, wherein the deuterium isotope is presentin an amount greater than 0.10% of the R_(x) hydrogen atoms.
 2. A methodof modulating the behavior of the citrus leafminer, Phyllocnistiscitrella, comprising: introducing a modulating composition to a field,wherein: the field, comprises: crops to be protected from the citrusleaf miner; the modulating composition, comprises: a composition ofclaim
 1. 3. The method of claim 2, wherein the composition, furthercomprises: a deuterium-enriched aldehyde of formula 60:


4. The method of claim 2, further comprising: harvesting the crops. 5.The composition of claim 4, further comprising: a deuterium-enrichedaldehyde of formula 60:


6. The method of claim 4, wherein the harvest is less damaged than thatfrom fields to which the modulating composition has not been introduced.7. An insect behavior modulating composition for modulating the behaviorof the cotton bollworm, Helicoverpa armigera, comprising: adeuterium-enriched aldehyde of formula 27:

wherein: there are at least 6×10¹⁸ molecules of the aldehyde in thecomposition; R_(x) is hydrogen, wherein the deuterium isotope is presentin an amount greater than 0.10% of the R_(x) hydrogen atoms.
 8. Thecomposition of claim 7, wherein the composition, further comprises: adeuterium-enriched aldehyde of formula 28:


9. A method of modulating the behavior of the cotton bollworm,Helicoverpa armigera, comprising: introducing a modulating compositionto a field, wherein: the field, comprises: crops to be protected from H.armigera; the modulating composition, comprises: a composition of claim7.
 10. The method of claim 9, wherein the composition, furthercomprises: a deuterium-enriched aldehyde of formula 28:


11. The method of claim 9, further comprising: harvesting the crops. 12.The method of claim 11, wherein the harvest is less damaged than thatfrom fields to which the modulating composition has not been introduced.13. An insect behavior modulating composition, comprising: adeuterium-enriched aldehyde of formula 315:

wherein: there are at least 6×10¹⁸ molecules of the aldehyde in thecomposition; R_(x) is hydrogen, wherein the deuterium isotope is presentin an amount greater than 0.10% of the R_(x) hydrogen atoms.
 14. Amethod of modulating the behavior of insects, comprising: introducing amodulating composition to a field, comprising: crops to be protectedfrom insects; the modulating composition, comprising: a composition ofclaim
 13. 15. The method of claim 14, further comprising: harvesting thecrops.
 16. The method of claim 15, wherein the harvest is less damagedthan that from fields to which the modulating composition has not beenintroduced.